Copolymers of alkenyl phosphorus esters as lubricating oil additives



I COPOLYMERS F v ALKENYL PHOSPHORUS ES- TERS AS LUBRICATING OlL ADDITIVES Peter Kirby, Kelsall, England, assi'gnor to Shell Oil Com- I pan)", New ork, N.Y., a corporation of Delaware No Drawing. Filed Aug. '30-, 1961, Ser. No. 134,851

36,950/60 2 Claims. (CL 252-49.s

This invention relates to lubricating compositions containingashless polymeric additives and to the additives themselves, particularly additives that improve the load carrying capacity of lubricating oils, and more particula'rly poly-functional additives that improve not only the load carrying capacity but also one or more other properties, e.g., the viscosity/temperature characteristics and the detergency of lubricating oils.

According to the present inventiom'lubricating oil compositions are provided which comprise a major portion of a lubricating oil and a minor proportion of a copolymer of (A) an alke'nyl substituted organic phosphorus compound and (B) a polymerizable-unsaturated ester which contains an oil-soluble hydrocarbyl radical of at least 8,

preferably 12 to 30 carbon atoms.

A further feature of the present invention is the provision of novel oil-soluble copolymer of an alkenyl sub- 'stituted organic phosphorus compound containing a phosphinylidyne group and a C alkyl methacrylate, The term phosphinylidyne group is to be construed throughout the present specification as meaning P-- O group (cl. Jour., Chem. Sec., 1952, page 5125).

Claims priority, application Great Britain, Oct. 27, 1960, I j

The alkenyl-substituted organo-phosphorus compounds containing a phosphinylidyne group of (A) may be derived from phosphoric acid, phosphonic acid, phosphinic acid or pho'spliine oxide. Thus a-very suitable class of phos phorus compounds is that have the general formula:

4 R20 ORi wherein at least one of the groups R R and R is an alkenyl or cycloalkenyl radical, and the other group(s) is (are) hydrogen, or an unsubstituted alkyl, cycloalkyl, aryl, aralkyl or alkaryl radical. The alkenyl radical may be u:flmono-olefinically unsaturated hydrocarbon radicals,

; e.g., vinyl or aor B-alkyl substituted vinyl radicals, but preferably are 18: mono-olefinically unsaturated hydrocarbon radicals of the formula -CR '-CR=CR' where R is a hydrogen atom or an alkyl group preferably having no more than 6 carbon atoms. The alkenyl radicals may be the same or different, but are preferably the same, if a dior trialkenyl. derivative is desired, and more preferably'they are allyl radicals. Alkenyl esters of phosphoric acid may be prepared by any method well-known in' the art. For example, the vinyl type esters may be prepared by dehydrohalogenation of compounds of the formula (XCH CH O) (RO) P O, where X is a halogen, which compounds may be themselves prepared by reactingphosphorus/halogen compounds with ethylene oxide.-

The allyl type esters can be prepared by reacting the desired phosphorus/halogen compound with a 5:7 mono olefinically unsaturated alcohol in the presence of an acidsequestrant, e.g., pyridine. Examples of suitable phosphoric acid esters are allyl dihydrogen phosphate, dibutyl allyl phosphate, diethyl allyl phosphate, diallyl hydrogen phosphate, diallyl methy phosphate, diallyl butyl phosphate, diallyl phenyl phosphate, di'allyl cyclohexyl phosphate, allyl methallyl hydrogen phosphate, divinyl hydrogen phosphate, divinyl ph'enyl phosphate, bis(2-ethylwhere at least one of the groups R;, R and R are alkenyl or cycloalkenyl groups and theother group(s') is(are) hydrogen, or an unsubstituted or substituted alkyl, cycloalkyl, aryl, alkaryl, or aralkyl radical. Preferably R at least should be an alkenyl or cycloalkenyl radical. The

alkenyl radicals may be out? mono-olefinically unsaturated hydrocarbon radicals, e.g., vinyl or y or fi-alkyl substituted vinyl radicals, but preferably the alkenyl radicals are B27 mono-oleflnically unsaturated hydrocarbon radicals of the formula -'CR -CR'=CR" where R is a hydrogen atom or an alkyl group preferably having up to six carbon atoms. The alkenyl radicals may be the same or different but are preferably the same, if a dior tri-alkenyl derivative is desired, more preferably they are allyl radicals. The above alkenyl derivatives of phosphonic acid may be prepared byany of the methods well-known in the art. For example, if R; and R are both alkenyl radicals, the dialkenyl .phosphonates may be conveniently prepared by reacting the desired phosphonic dihalide with the desired mono-olefinically unsaturated alcohol in the presence of an acid-sequestrant, e.g., pyridine, to produce the diester. When R andR are alkenyl radicals, the desired compounds may be prepared by an Arbuzov reaction on a dialkyl alkenyl phosphite with an alkenyl halide. Where R is the only alkenyl radical present, the required compound may be prepared by reacting the phosphorus trichloride with analkanol to produce a trialkyl phosphite which may then be reacted with an alkenyl halide to produce the required mono-alkenyl derivative.

Examples of suitable alkeriyl derivatives of phosphonic acid are diethyl allylphosphonate, allyl butyl hydrogen p p yl phenylphosphonic acid, diallyl phenylphosphonate, diallyl ethylphosphonate, diallyl'butylphosphonte, divinyl ethylphosphonate, the mono-allyl ester of allylphosphonic acid, allyl methallyl phenylphosphonate,

dicrotyl hydrogenphosphonate, diallyl benzylphos'phonate,

divinyl phenylphosphonate, di(2-pentenyl)ethylphosphonate, and diallylallylph osphonate.

A further class of alkenyl phosphorus monomers that i formula --CR' CR=CR' where R is a hydrogen atom or an alkyl group preferably having up to six carbon atoms. The alkenyl radicals may be the same or different but are preferably the same where a dior trialkenyl derivative is desired, more preferably they are allyl radicals. The above' alkenyl derivatives of phosphinic acid Patented Sept. 28, 196s saturated alcohol. "dialkenyl derivative is desired having both alkenyl radimay be readily prepared by any of the methods known in the art. I

If R is alkenyl the 18: mono-olefinically unsaturated derivatives may be prepared by direct esterification of a phos'phinic acid with the desired 8:7 mono-olefinically un- Alternatively,= if R is alkenyl and a I unsaturated alcohols'or acids having at least an 8"carbon,

.calsthe same, a convenient method of preparation is to react; a phosphonous. dichloride with the desired B2 I ture by distillation.

'- If Rg and R3 are alkenyl radicals, thevdesired product preferably a 12-18 chain in the molecule such as esters of unsaturated alcohols (vinyl or allyl) and saturated C lmaliphatic carboxylic acids such'as vinyl decanoate,

vinyl laurate, vinyl tridecanoate,'vinyl myristate, vinyl pentadecanoate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl nonadecanoate; vinyl arach'idate, vinyl beheuate, vinyl 4,5,tS-trimethyldodeeanoate, vinyl 6,8,10-

I triethyl tride'canoate,'vinyl 12-hydroxystearate, vinyl 9,10-

may be obtained by reacting thedialkenyl phosphinous halide with a suitable alcohol or phenol in the presence of an acid sequestrant, e.g.,*dimethyl aniline. Examples of alkenyl derivatives of phosphinic acid are-allyl phosf phin'ate, the allyl ester of phenylethylphosphinic acid, the allyl ester of phenyl allyl phosphinic acid, the allyl ester of allyl phosphinic acid, the: vinyl ester ofvinylphenylphosphinic acid, diallyl phosphinic acid, allyl phenylphosphinic acid, allylmethallylphosphinic acid, ethyl .di-

allylphosphinate, phenyl allylphosphinate, methyl allyl-' methallylphosphinate and allyl diallylphosphinate'.

' A still further class of 'alkenyl phosphorus compounds useful in the presentinvention isthat havingthe general formula!- v I Bi V 0 where at least one of R R and R are alkenyl or cycloal'kenyl radicals and the other group'(s) is(are) hydrogen or. an alkyl,-cycloalkyl, aryl, aralkyl, or alkenylradicals may be'azfl mono-olefini'cally-unsaturated hydrocarbon radicals,.e.g., vinyl or aorp-alkyl substituted vinyl radicals', but preferably are pry mono-olefinically unsaturated-hydrocarbon radicals, of the formula CR' -CR'=CR.', r

where R is a hydrogen atom-or an alkyl preferably having up to six carbon atoms. The alkenyl'radicals may be the same 'or different, but preferably they'are the'same if a dior tri-alkenyl derivative is desired and more preferably-they'are allyl-groups. Such phosphine oxides may readily be-prepared by the reaction between a monoor dihalophosphine o'r"phosphorus trichloride and the desired alkenyl Grignard'reageut followed by air oxidation. Alternatively, such compounds maybeprepared by reacting a compound of the formula R;,RX where R is aryl or. alkyl' or 'alkenyl and n is 1 or 2, with sulfur dioxide and chlorine to produce ,R P(O)X and then reacting this product with alkenyl Grignard reagent. Exemplary of suitable phosphineoxides are allyl butyl phenyl phosphine oxide, diallyl p-methoxyphenyl phosphine oxide, diallyl phenyl phosphine oxide, diallyl sec-butyl phosphine oxd-ihydroxystearate, vinyl chlorostea-rate, 'vinyl ,cyanostearate, vinyl acetylstearate, allyl palmitate or esters ofsaturated alcohols and unsaturated acrylic acids such as C alkyl 'acrylate or methacrylate, e.g., decyl 'acrylate, lauryl acrylate, stearyl acrylate, dec'yl methacrylate, lauryl. methacrylate, cetyl 'methacrylate, stearyl methacrylate,

eicosanyl acryla'te, docosanyl acrylate' andv the like, and

mixtures thereof. Mixtures of. monomers (B) may be used in preparing the copolymers of this inventionto which may bealso incorporated a small amount (5-30% of the total polymer) of anacrylate ester of an acrylic acid anda Ci, alkanol and mixtures of esters containing a C 4 alkyl group maybe used. illustrative examples of such mixed esters include decylmethacrylate/octadecyl methacrylate; tetradecyll methacrylate/hexadecyl methide, divinyl phenyl phosphine oxide, diallyl butylqphosphine oxide, diallyl benzyl phosphine oxide, diallyl chlormethyl phosphine oxide, allyl methallyl phenyl phosphine oxide, "dimethallyl phenyl phosphineoxide, dimethallyl idopro'pyl phosphine oxide and tr-iallyl phosphine oxide.

Mixtures of two or more of the foregoing monomers. can-be used if desired) Where it is desired to include the oleophilic hydrocarbon chain of atleast 8 carbon atoms inthe phosphorus containing monomer, this can readily be done for example, 'by a reacting compound having the formula (R0) (A)P(O)H where A may be ary1, alkyl, alkoxy, aroxy or hydrogen, and R is alkyl or 'aryl, with an olefin having at least 8 carbon atoms in the presence of a free radical initiator. The product can then-be transesterified to replace, the alkoxyfo'r aroxy group(s) by unds of (B) include esters of acrylate; tetradecyl acrylate/octade'cyl methacrylate;

dodecyl methacrylate/eisonsanyl acrylate; vinyl laurate/ vinyl stearat'eand the like. I

When mixtures of higher acrylate esters are used, it is highly desirable to, have a substantial difference in the number of carbon atoms of the alcohol'portion.- Particularly superior results are obtained when one of the acryl ate esters if a C to C acrylate ester and theother is a C to C acrylate ester,

' In the mixtures, the different long chain acryla'te esters are employed in molratios 'from 1:4 to 4:1. The superior copolymers are obtained'when the higher ester, e.g., those having from 10 to 20 carbon atoms in the alcohol portion, and'the lower esters, e.g., those having from '10 to 14 carbon atoms in the alcoholportion are combined in a mol ratio varying from 1:1 .to,1:3. v i

If desired the copolymers' of the present invention can be modified by replacingx5-20% of the polymerizable ester (B) with other polymerizable mono-olefinic phosphotons-free compounds having an oleophilic hydrocarbon chain of at least 8 carbon atorns such as vinyl 'ethers such as vinyl octyl ether, vinyl'lauryl ether, vinyl dicresyl ether,vinyl ketonessuch as octylvinyl ketone, lauryl vinyl ketone, and stearyl vinyl ketone, vinyl aryl compounds such as orthooctyl styrene, para-lauryl styrene, para-stee ryl styrene, para-cetyl styrene and other alkyl derivatives of styrene in which a C malkyl group-or groups may be substituted in the ring or in the side chain or both;alpha, beta-unsaturated polycarboxylicacids'and their derivatives such as maleic, fumaric, citraconic, itaconic, crotonic, aconitic and tricarballylic acids andtheirmono-polyestcrs with aliphatic and aromatic alcohols, and their amides and. nitriles, mayalso be used or u-oletins particularly those havingmore than 8 and preferably 12-20 carbon atoms, e.g.',- e-octadecene; amino-substituted olefins, e.g., p-(fi-dioctylarninoethyl) styrene and nitrogen-containing heterocyclic compounds having a monoolefinically unsaturated substituent, e.g., the vinyl pyridines (whether 2, 3 or 4-substituted) suchfas vinyl C alkyl pyridine, 3-lauryl-5-vinylrpyridine, 4-'stearyl-2-vinyl pyridine-and 2- stearyl-S-vinyl pyridine. Vinyl lactams are also suitable monomers, particularly'the' N-vinyl pyrrolidones .or N- vinyl piperidones. These vinyl compounds should have at least one C 4 alkyl radical in the-molecule.

The molar ratio of phosphorus containing monomer (A) to the pol'ymerizable ester (B) may vary within wide limits and generally'between 20.11 and 1:20. Preferably the ratio lies between 1:1 and 1:20, with ratios between l:3 and 1:10 being especially suitable, of which 5--20% of thepolymerizable ester (B) may be replaced with any of the above mentioned phosphorous-free polymerizable ml. ether over a period of two hours;

compounds, e.g., vinyl octylether, substituted vinyl pyridine or pyrrolidone, e.g., 4-stearyl-2-vinyl pyridine.

The copolymers of the invention can b'e'prepared by any suitable means. Normally the reactants are'copolymerized in the presence of a catalyst. Oxygen-yielding catalysts, such as organic peroxides, may be used. These may be aliphatic, aromatic, heterocyclic, or alicyclic peroxides, such as diethyl peroxide, tertiary butyl hydroperoxide, di(tertiary butyl)peroxide, benzoyl peroxide, dimethyl thienyl peroxide, dilauroyl peroxide and urea peroxide. Other catalysts include sodium bisulphite, diethyl sulphoxide, ammonium persulfate, alkali metal perborates and azo compounds, e.g., azo-(bis-isobutyro)nitrile. The catalysts are generally sed in an amount of'0.1 to 5% by weight of the reactants.-

copolymers have a molecular weight in the'range of from 25,000.-to 1,000,000, 50,000 to 400,000.

. The'following examples illustrate the production of copolymers of the present invention.

EXAMPLE I I A-solution of 277 g. of allyl alcohol, 326 g. pyridine and Y280 ml. of ether wascooled to approximately -30 C. by means of a .bath of IPA/CO and was then added to a solution of 255 g. phosphorus oxychloride in 132 After the first hour a further 100 ml. of ether was added to facilitate preferably in'the range of from stirring. The reaction mixture was stirred for a furtherthree hours after which time the pyridiniurri chloride formed with filtered ofl. The filtrate was evaporated leaving triallylphosphate as a clear yellow oil.

51 g. of the triallylphosphate was dissolved in 100 mls. of IMS and refluxed with 100 mls. of 5 N aqueous solution hydroxide for two hours. The solvents were then removed under reduced pressure (100 C./15 mm.) and the residual oil was extracted withether in order to remove unhyd-rolysed phosphate. The oil was then treated with dilute hydrochloric acid until acid and the oil thus separated was extracted with ether to produce diallyl hydrogen phosphate.

'A mixture of 3.4 g. of the diallyl hydrogen phosphate and 25 g. of lauryl methacrylate in 15.5 g. of technical white oil and 20 ml. of benzene was treated with 0.5 g. benzoyl peroxide and treated at 70 C. for 18 hours with stirring. The benzene was then evaporated to leave the copolymer in a solution of white oil. The molecular ratio .of the diallyl hydrogen phosphate to lauryl methacrylate in the copolymer was 1:6.

, EXAMPLE II Phenylphosphonous dichloride was prepared by refluxingv together 525 'mls. phosphorus trichloride, 468 mls. benzene and 300 g. of aluminum chloride for four hours. Phosphorus oxychloride (223 mls.) was then added and the mixture briefly refluxed. Excess benzene and phosphorus trichloride'was evaporated under vacuum and the residue cooled toabout 40 C. and extracted with ligroin. From the extract, crude phenylphosphonous dichloride was removed and purified by redistillation under reduced A solution of 60.5 g. of allyl bromide in 285 ether was added dropwise to 12 g. magnesium in 100 mls. ether. After stirring for 1 hour, 23 g. of phenylphosphonous dichloride in 100 mls. of ether was added and the mixrated.

The resultant crude diallylphenylphosphine was purified 'by redistillation. All these operations were conducted in a nitrogen atmosphere.

5.5 g. of the diallylphenylphosphine was dissolved in 12 mls. of benzene and air passed through the solution for thirty minutes to produce diallyl phenyl phosphine oxide. To this solution was added 23 ml. benzene, g. of technical white oil, 7 g. of lauryl. methacrylate and 0.5 g. of

benzoylperoxide. The mixture was heated to 75 C and stirred for 24 hours. At the end of each of the first three hours, a further amount of 7 g. lauryl methacrylate was. added and with the third addition, a further 0.5 g. of

j benzoyl peroxide was added. The benzene was evaporated at reduced pressure and the residue heated at C./1 mm. Hg for 30min'utes. The' resulting copolymer solution of diallyl phenyl phosphine oxide and lauryl methacrylate in technical white oil was soluble in mineral oil. The molecular ratio of diallyl phenyl phosphine oxide to lauryl methacrylate was 1:4.

EXAMPLE 111 tion until the exothermic reaction was complete. The A product was filteredwhilst cool to give a residue of phenyl phosphonic tetrachloride. Further quantities of this material was-obtained *by evaporation of the mother liquors. The product. was purified by recrystallization from car bon tetrachloride, followed by drying in a vacuum desiccator. t

Phenyl phosphonic tetrachloride (63 g.) was dissolved in benzene (250 ml.) and the stirred mixture treated with sulfur dioxide until reaction was complete. The reaction is rapid and the phenyl phosphonic dichloride, Ph.POCl produced was recovered by distillation B.P. 87 C./ 1mm. Hg. Phenyl phosphonic dichloride (49 g.) was added slowly with stirring to a solution of allylalcohol (29 g.) and pyridine (40 g.) in ether (250 ml.) cooled to 0 C. The rate of addition was such that the temperature ofthe mixture remained at 0 C. Stirring was continued'for 2 hours after complete addition. The reaction productwas filtered to remove pyridine hydrochloride and the residue washed with 200 ml.- ether. The ether was evaporated from the filtrate and the residue distilled to give diallyl phenyl phosphonate, B.P. 112 C./0.3 mm. Hg.

To the solution of diallyl phenyl phosphonate (5.9 g.) and lauryl methacrylate (25.4 g.) in mineral oil (15.5 g.) at C., ditertbutyl peroxide (0.4 ml.) was added and the whole stirred vigorously. The solution was maintained under these conditions for 5 hours. The product had a molar ratio of 1:4.diallyl phenyl phosphonate to lauryl methacrylate and was a 66.7% concentrate in mineral oil. This concentrate was readily oluble in further samples of mineral oil.

EXAMPLE IV (168 g.) in diethyl ether (2000 ml.) phenyl. phosphonous dichloride was added slowly with stirring. The rate of additionwas adjusted to maintain a gentle reflux. Stirring and refluxing were continued for a further two hours after complete addition. Pyridine hydrochloride was filtered OE and the residue washed with more ether (500 ml). The ether was evaporated from the filtrate and the product distilled, the bulk of the material (allyl phenyl allylphosp'hinate) boiling at 102 C./0.4 mm. Hg. Small amounts of diallyl phenylphosphonite are separated during the distillation, B.P. 79 C./0.4 mm. Hg.

To a solution of allyl phenyl allylphosphinate (6 g.) and lauryl methacrylate-(28 g.) in mineral oil (68 g.) at 140-S C. -di-tert-butyl peroxide (0.4 ml.) was added and the whole stirred vigorously for 24 hours. The prodnot was heated at l'C./0.5 mm. Hg for 30 minutes 'but no distillate was obtained. This product had a 1:4

molar ratio of allyl phenyl allylphosphinate 'to lauryl v methacrylate and was a 33.3% concentrate in mineral :0il. Y 1

EXAMPLE V r 1 151.2 gm; of phosphorus trichloride was added to a so- I '1 lution of 151.8 gm. of ethanol and 268 gm. of pyridine in 151.8 :gm. of a petroleum ether boiling at 60-80 C.,

over a period of two hours, II he temperature was maintained at 0-5-* 0; 'by a Cardice/IPA cooling bath. The

vreaction mixture was stirred for a further hour after complete addition, during this time the, mixture was allowed to warm to'room temperature. The product was filtered to remove pyridine hydrochloride and the solvent and phosphorus trichloride were then stripped from the ,filtrate. The residue was distilled to give triethyl phosphite.

121 gm. of allyl bromide containing a small quantity i of hydroquinone was refluxed in a 50 ml. flask-under a 10 inch column packed with glass beads, 140 gms. of triethylphosphite was. added starting at a rate which maintained me'rs 1:4.

methanol by decanting and'strip pin-g of solvent underreduced pressure to yield a clear oil soluble copolymer (575. y

g.) of triallyl phosphate and'lauryl methacrylate. Phosphorous contentof copolymeri- 1.08%, ratio of mono The copolymers of the present "invention are particularly useful as additives in lubricating compositions, and such compositions are a furthenfeature of the present invention a The lubricating oil to whichthecopolymers maybe added to provide lubricating compositions of the invention can be any natural or synthetic oil having lubricating properties. Thus, the oil canbe a hydrocarbon lubricatphthalate and trioctyl phosphate and po'lyalkyl silicone a steady reflux. Material bo'ilin'g at 3739 C. was run I off frorn'a weir head'at the-topof the column. After 8 7 hours, no more low boiling material. -re'maine d; and the p reaction mixture was distilled to produce diethyl allyl.- Y

Y phosphonate."

133,5 gms. o diethyl allylphosphonate, 190.5 gms.

lauryl methacrylate, 445 gms. of a SAE 10W30'grade ,mineral oil and 7.5 gms.,of di-tert-butyl' peroxide were mixed and stirred together at 145 C. Afterl hour a further-quantity of 190.5 gms. laurylmethacrylate was added, this was'repeated after 2 hours and. again after l 4 hours. I This product was then stirred for a further g90'irninutes. The mixture was then stripped at 140 C. -and 0.15 mm. Hg pressure and a residue consisting-of a 66.6% 'concentrate of aucopo'lymer of diethyl allyl phosphonate and 'l'auryl methacrylate in a molar'ratio of 1:8 in the mineral oil'was recovered. r EXAMPLE v1 557 gms. of allyl alcohol, 7 24 gins. of pyridine and 500 mls. of sodium dried toluene were stirred at 0-5 C.

p 413 gms. 'of phosphorus trichloride'in 100 mlsfof sodium driedtoluenewas then added whilst maintaining the temperature of 0-5 C. The product was stirred for /2 hour and'then the amine hydrochlor'ide'was filtered olf.

The toluene was then stripped on leaving triallyl phosphi-te.

48 gms. of nbutyl bromide containing'a'small amount r or: 'hydroquinone was heated to reflux 'in a vessel fitted with a column packed with glass beads surmounted by a weir'head; 220' gms. of triallyl phosphite was added and refluxing continued for ,20 hours and material boiling below 97 C. was removed. Excess butyl bromide was .then distilled oif and the-residue comprised diallyl butylphosphonate. 109 gms. of diallylbutylphosphonate, 508

gms. of'lauryl methacrylate, 927 gms. of an SAE l0W30 grade mineral oil and 7.6 gms. of di-tert butyl peroxide s were heated at 145 C. for 4 hours. The final product was a 40% wt. concentrate in'the oil of a 'copolymer of EXAMPLE VH 127 g. of the triallyl phosphate prepared as inExample I, lauryl' methacrylate (191-g'.) and 'benzoyl peroxide (7 'g.-) in dry benzene (200 ml.) were stirred for 1 hour at 75 C. Lauryl methacrylate (400 g.) was added to the stirred mixture over 7 hours and stirring continued" for 16 hours after completing the addition. The temperature remained at 75 -78 throughout; Most of the solvent was removed under reduced pressure-and the viscou residue poured with vigorous stirring, into methanol (2000 1111.). The precipitated copolymer was washed with v by weight based on the, total compositiomgenerally from t polymers such as diniethyl silicone polymers. If desired, the synthetic lubricating oils may be used'as the sole base lubricating oil or admixed with fatty oils-or derivatives thereof.

ln the lubricating compositions of 'prese'ntinvention the polymeric additive is present-in va minor proportion 0.01% to 20% and preterablyirom 0.1% to 8% by weight. v I

It will be understood that the lubricating compositions of'the'inv'ention may be. modified by the addition thereto of minor proportions (0.1-2%) of other additives such as metal dithiophosphates, e.g., zinc di- 2-ethylhexyl dithiophosphate, metal organicsulfonates, e.g., neutral or basic calcium, barium or zincpetroleum sulfonate; metal thiocarbamates, e.g.,,zinc, chromium or'calcium dibutyl or. diamyl dithiocarbamate; amines, e .g., phenyl-al hanaphthylamine or octadecylam ne; alkylatedphenols and alkylated bisphenols, e.g., 2-.6 dietertiary-butyl 4-methylphenol and 4,4'methylene bis( 2,6-'dietertiarybutyl phenol);

' organic sulfides, e.g., dibenz'yldisulfide.

Lubricating compositions of the present invention are useful as engine oils, gear oils, turbine oils and in various other fields of lubrication where good detergency, viscosity/ter'nperature characteristics 'andload carrying properties are-essential. t

, diallyl butylphosphonate and lauryl methacrylate having I a'monomer ratio of'lz l. I r

'Copolymer of diallyl hydrogen phosphate/lauryl I 'Mineral oil I Mineral oil Compositions of "this invention. are illustrated by the following formulations;-the ratios in-brackets being the mole 'ratiosof themonorners used for preparing the copolymers. The mineral lubricating oil ,used is mg a viscosity of 10 cs. at-210 F.

' Composition A methacrylate (1:6) 4% wt. Balance Composition B Copolymer of vdiallyl hydrogen pho'sphate/lauryl methacrylate (1:8) 4% wt.

Mineral oil Balance ComposiiionC Copolymer of diallyl phenyllphosphine oxide/ lauryl methacrylate (1:4). Mineral oil Balance CompositionD' Copolynier of the allyl ester oflph e nylallyl phosphinic acid/lauryl methacrylate (1:4) 2.0% wt. 4, et ylene'-bis(2,6-di-tert.butyl' phenol) 0.75% wt. Balance n a a Composition E Copolymer diallyl phenyl phosphonate/lauryl' methacrylate (1:4) 6.8% wt. Mineral oil Balance Composition'F Copolymer of diallyl phenyl phosphine oxide/ lauryl methacrylate (1:4) 3.9% wt. 4,4-methylene-bis(2,6-ditertiarybutylphenol) 0.75% wt. Mineral oil Balance Composition G Copolymer' of diethyl' allyl phosphonate/lauryl methacrylate (1:.8) 2% wt. 4,4-methylene-bis(2,6-ditert.butyl phenol) 0.75% wt. Mineral oil Balance Composition-H Copolymer of diallyl butyl phosphonate/lauryl methacrylate (1:4) 2% wt. 4,4'-methylene-bis(2,6-ditert.butyl phenol) 0.75% wt. .Mineral oil Balance Composition I Copolymer of triallyl phosphate/lauryl methacrylate (1:4) 2% wt. 4,4'-methylene-bis(2,6-ditert.butyl phenol) 0.75% wt. Mineral oil Balance In order to illustrate the properties of lubricating compositions and the utility of copolymers according to the present invention, certain compositions were subjected to tests in the following manner.

,The thickening ability of the copolymers used as adresults are contained in Table I.

TABLE I Concen- Copolymer tratlon; VT

percent wt.

Diallyl hydrogen phos hate/laifil methacrylate (1:6). 4 109 Allyl ester of phenylal yl phosp nlc acid/lauryl methaerylate (1: 4.1 117 Dlallylphenyl phosphine oxide/lauryl methacrylate These figures represent good thickening properties. The dispersant properties of various compositions were illustrated in the following manner. 7

1 part by weight of used straight mineral oil from a diesel engine and containing about 2% w. of oil-insolubles was mixed with 5 parts of the unused mineral aid of Compositions A-I. In this blend the insoluble particles were clustered; Other blends were made containing, as before ,4; of used oil, and the remaining a series of increasing concentrations of one of the additives in the unused mineral oil. At a particular concentration the insoluble particles become dispersed, and this concentration is taken as a measure of the dispersancy of the additive,

i.e., the lower the concentration, the better are the dispersance characteristics. Some results are given in Table II. 7

TABLE 11 CConnin. o1 opo yme! I required to Copolymer disperse clusters In mg.- per g. blend Dlallyl phosphatellaurglnmethacrylate (1:6) 0. 4 Diallyl phenyl phosp e oxidellauryl methacrylate 0 3 methyl allylphosphonate/lauryl methae'rylate (1:4). 01s Triallylphosphate/laurylmethacrylate (1:4) 1.7 Dlethyl ellylphosphonate/lauryl methaerylate (1:8) 0. 67 Diallyl phenylphosphonate/lnuryl methserylate (1 :4) 1. 0 Dlgiutyl allyl phosphino oxide/lauryl methacrylate 0 4 A mixture of dlallyl butylphos honate and dlallyl phosphate in 9:1 molar ratlofiauryl methacrylate o 67 A mixture of diallyl hutylphos honate and diallyl plhtgphate in 4:1 molar ratiolqauryl methacrylate O 67 ditives in the present invention was assessed in terms of Compositions D, F, G, H and I exhibited good low tappet scutfing is indicativeof the load carrying capacity of the oil. Compared with a similar'formulation, but in which the copolymer according to the invention is replaced by 4% wt. of a copolymer of laurylmethacrylate and vinyl pyrrolidone, composition F exhibits a 60% reduction in the amount of tappet scuffing and an 83% reduction in cam wear and Composition H exhibits a 50% reduction in the amount of tappet scuffing and a reduction in cam wear. Also, Compositions A and D, when subjected to a test for extreme pressure properties on the 4-bal1 machine, exhibited 2% second seizure delayloads of 137 kg. and 92 kg. respectively compared with 65 kg. for the base oil.

I claim as my invention:

1. A mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.01% to about 20% of an oil-soluble copolymer of triallyl phosphate and C alkyl methacrylate, in

the moi ratio of 1:20 to 20:1,. respectively, said copolymer having molecular weight of from about 50,000 to 4 2. A mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.01% to about 20% of an oil-soluble copolymer of triallyl phosphate and laudyl methacrylate in the mol ratio of 1:20 to 20:1, respectively, said copolyiner having a molecular weight of from about 50,000 to 1,000,000.

References Cited by the Examiner UNITED STATES PATENTS DANIEL E. WYMAN, Primary Examiner. JULIUS GREENWALD, Examiner. 

1. A MINERAL LUBRICATING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF MINERAL LUBRICATING OIL AND FROM ABOUT 0.01% TO ABOUT 20% OF AN OIL-SOLUBLE COPOLYMER OF TRIALLYL PHOSPHATE AND C8-20 ALKYL METHACRYLATE, IN THE MOL RATIO OF 1:20 TO 20:1, RESPECTIVELY, SAID COPOLYMER HAVING MOLECULAR WEIGHT OF FROM ABOUT 50,000 TO 1,000,000. 